Tetrametallic bulk hydroprocessing catalysts

ABSTRACT

Bulk catalysts comprised of nickel, molybdenum, tungsten and titanium and methods for synthesizing bulk catalysts are provided. The catalysts are useful for hydroprocessing, particularly hydrodesulfurization and hydrodenitrogenation, of hydrocarbon feedstocks.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of U.S. ProvisionalApplication Ser. No. 63/019,479, filed May 4, 2020.

FIELD

This disclosure relates to tetrametallic bulk catalysts for use inhydroprocessing of hydrocarbon feeds, as well as methods for preparingsuch catalysts.

BACKGROUND

The hydroprocessing of hydrocarbon feedstocks generally encompasses allprocesses in which a hydrocarbon feedstock is reacted with hydrogen inthe presence of a catalyst and under hydroprocessing conditions,typically, at elevated temperature and elevated pressure.Hydroprocessing includes processes such as hydrodesulfurization,hydrodenitrogenation, hydrodeoxygenation, hydrodemetallation,hydrodearomatization, hydrogenation, hydrogenolysis, hydrotreating,hydroisomerization, and hydrocracking.

Hydroprocessing catalysts usually comprise one or more sulfided Group 6metals with one or more Group 8 to 10 non-noble metals as promoters on arefractory support, such as alumina. Hydroprocessing catalysts that areparticularly suitable for hydrodesulfurization, as well ashydrodenitrogenation, generally comprise molybdenum or tungsten sulfidepromoted with a metal such as cobalt, nickel, iron, or a combinationthereof.

In addition to supported catalysts, hydroprocessing using bulk catalysts(also referred to as “unsupported” catalysts) are also known. Althoughbulk hydroprocessing catalyst compositions have relatively highcatalytic activity relative to conventional supported hydroprocessingcatalysts, there exists a continuous need in the art to develop novelbulk catalyst compositions with further improved hydroprocessingactivity.

SUMMARY

In a first aspect, there is provided a bulk catalyst precursorcomprising: (a) 1 to 60 wt. % of Ni, on a metal oxide basis; (b) 1 to 40wt. % of Mo, on a metal oxide basis; (c) 5 to 80 wt. % of W, on a metaloxide basis; and (d) 2 to 45 wt. % of Ti, on a metal oxide basis.

In a second aspect, there is provided a sulfided bulk catalystcharacterized in that it is the bulk catalyst precursor described hereinthat has been sulfided.

In a third aspect, there is provided a method for preparing the bulkcatalyst precursor described herein, the method comprising: (a)combining in a reaction mixture: (i) a Ni-containing precursor; (ii) aMo-containing precursor; (iii) a W-containing precursor; (iv) aTi-containing precursor; (v) optionally, an organic compound-basedcomponent; and (vi) a protic liquid; and (b) reacting the mixture underconditions sufficient to cause precipitation of the bulk catalystprecursor; wherein the steps to prepare the bulk catalyst precursor arecarried out at a temperature of no more than 200° C.

In a fourth aspect, there is provided a method for preparing the bulkcatalyst precursor described herein, the method comprising: (a)combining in a reaction mixture: (i) a Ni-containing precursor; (ii) aMo-containing precursor; (iii) a W-containing precursor; (iv)optionally, an organic compound-based component; and (v) a proticliquid; and (b) reacting the mixture under conditions sufficient tocause precipitation of an intermediate bulk catalyst precursor; and (c)compositing the intermediate bulk catalyst precursor with aTi-containing precursor to form the bulk catalyst precursor; wherein thesteps to prepare the bulk catalyst precursor are carried out at atemperature of no more than 200° C.

In a fifth aspect, there is provided a process for hydroprocessing ahydrocarbon feedstock, the process comprising contacting the hydrocarbonfeedstock with hydrogen in the presence of a bulk catalyst athydroprocessing conditions to give at least one product, wherein thebulk catalyst is a derived or derivable from a catalyst precursorcomprising: (a) 1 to 60 wt. % of Ni, on a metal oxide basis; (b) 1 to 40wt. % of Mo, on a metal oxide basis; (c) 5 to 80 wt. % of W, on a metaloxide basis; and (d) 2 to 45 wt. % of Ti, on a metal oxide basis.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a quaternary phase diagram with the fractional coordinatesof the vertices that define the polyhedral Ni—Mo—W—Ti composition space,according to an aspect of the present disclosure.

FIG. 2 shows a quaternary phase diagram with the fractional coordinatesof the vertices that define the polyhedral Ni—Mo—W—Ti composition space,according to an aspect of the present disclosure.

FIG. 3 shows an isotherm plot of N₂ physisorption conducted at 77 K onthe Ni—Mo—W—Ti catalyst precursor of Example 4.

FIG. 4 displays High-Angle Annular Dark-Field Scanning TransmissionElectron Microscopy (HAADF-STEM) images obtained for the Ni—Mo—W—Ticatalyst precursor of Example 4.

FIG. 5 shows an isotherm plot of N₂ physisorption conducted at 77 K onthe Ni—Mo—W—Ti catalyst precursor of Example 5.

DETAILED DESCRIPTION Definitions

The term “bulk”, when describing a mixed metal catalyst composition, maybe used interchangeably with “unsupported”, meaning that the catalystcomposition is not of the conventional catalyst form which has apreformed, shaped catalyst support which is then loaded with metals viaimpregnation or deposition catalyst.

The term “atmospheric pressure” is used herein to describe an earth airpressure wherein no external pressure modifying means is utilized.Generally, unless practiced at extreme earth altitudes, “atmosphericpressure” is about 1 atmosphere (about 14.7 psi or about 101 kPa).

The terms “weight percent,” and “wt. %”, which can be usedinterchangeably, indicate the percent by weight of a given componentbased on the total weight of the composition, unless otherwisespecified. That is, unless otherwise specified, all wt. % values arebased on the total weight of the composition. It should be understoodthat the sum of wt. % values for all components in a disclosedcomposition or formulation are equal to 100.

Bulk Catalysts and Bulk Catalyst Precursors

Tetrametallic bulk catalyst precursor compositions comprising oxides ofNi, Mo, W, and Ti are provided. Prior to use for hydroprocessing, thecatalyst precursor can be sulfided which converts metals to metalsulfides. After sulfidation, the composition corresponds to/is definedas a “catalyst” for the purposes of the claims below.

The bulk catalyst and/or corresponding bulk catalyst precursor comprisesnickel (Ni), molybdenum (Mo), tungsten (W) and titanium (Ti) metals. Thebulk catalyst and/or corresponding bulk catalyst precursor may containfrom 1 to 60 wt. % of Ni, such as from 5 to 40 wt. % or from 20 to 60wt. %, on a metal oxide basis; from 1 to 40 wt. % of Mo, such as from 1to 25 wt. % or from 3 to 20 wt. %, on a metal oxide basis; from 5 to 80wt. % of W, such as from 10 to 35 wt. % or from 20 to 75 wt. %, on ametal oxide basis; and from 2 to 45 wt. % of Ti, such as from 5 to 40wt. %, from 10 to 35 wt. % or 20 to 30 wt. %, on a metal oxide basis.Thus, the bulk catalysts disclosed herein can have the nomenclatureNi—Mo—W—Ti wherein each metal is present in amounts specified above.

In some aspects, the bulk catalyst and/or corresponding bulk catalystprecursor may be defined by a region of a quaternary phase diagramwherein the region is defined by ten points ABCDEFGHIJ and wherein theten points, on a metal oxide basis (wt. %), are: A (Ni=0.39, Mo=0.00,W=0.41, Ti=0.2), B (Ni=0.08, Mo=0.00, W=0.72, Ti=0.2), C (Ni=0.09,Mo=0.17, W=0.54, Ti=0.2), D (Ni=0.31 Mo=0.25, W=0.24, Ti=0.2), E(Ni=0.40, Mo=0.14, W=0.26, Ti=0.2), F (Ni=0.34, Mo=0.00, W=0.36,Ti=0.3), G (Ni=0.07, Mo=0.00, W=0.63, Ti=0.3), H (Ni=0.08, Mo=0.15,W=0.48, Ti=0.3), I (Ni=0.27, Mo=0.22, W=0.21, Ti=0.3), and J (Ni=0.35,Mo=0.12, W=0.23, Ti=0.3), such as depicted in FIG. 1 .

In some aspects, the bulk catalyst and/or corresponding bulk catalystprecursor may be defined by a region of a quaternary phase diagramdefined by eight points ABCDEFGH and wherein the eight points, on ametal oxide basis (wt. %), are: A (Ni=52.5, Mo=3.5, W=14, Ti=30), B(Ni=38.5, Mo=17.5, W=14, Ti=30), C (Ni=21, Mo=17.5, W=31.5, Ti=30), D(Ni=35, Mo=3.5, W=31.5, Ti=30), E (Ni=60, Mo=4, W=16, Ti=20), F (Ni=44,Mo=20, W=16, Ti=20), G (Ni=24, Mo=20, W=36, Ti=20), and H (Ni=40, Mo=4,W=36, Ti=20), such as depicted in FIG. 2 .

The molar ratios of metals in the bulk catalyst and/or correspondingbulk catalyst precursor can in principle vary between wide ranges. Themolar ratio of Ti/(Ni+Mo+W) in the bulk catalyst and/or correspondingbulk catalyst precursor can be in a range of from 10:1 to 1:10 or from3:1 to 1:3. The molar ratio of Ni/W in the bulk catalyst and/orcorresponding bulk catalyst precursor can be in a range of from 10:1 to1:10. The molar ratio of W/Mo in the bulk catalyst and/or correspondingcatalyst precursor can be in a range of 100:1 to 1:100.

The bulk catalyst precursor is a hydroxide and may be characterized ashaving the following chemical formula:

A_(v)[Ni(OH)_(x)(L)^(p)_(y)]_(z)[Mo_(m)W_(1-m)O₄][Ti(OH)_(n)O_(2-n/2)]_(w)

wherein: (i) A is an alkali metal cation, a rare earth metal cation, anammonium cation, an organic ammonium cation, phosphonium cation, or acombination thereof; (ii) L is an organic compound-based component; and(iii) 0≤y≤2/p; 0≤x<2; 0≤v<2; 0<z; 0<m<1; 0<n<4; 0.1<w/(z+1)<10.

The bulk catalyst precursor may be comprised of at least 60 wt. % (atleast 70 wt. %, at least 80 wt. % or at least 90 wt. %) of oxides of Ni,Mo, W, and Ti prior to sulfiding to form a bulk catalyst. In any aspect,the bulk catalyst and/or corresponding bulk catalyst precursor maycontain 40 wt. % or less of a binder material. Binder materials may beadded to improve the physical and/or thermal properties of the catalyst.

The bulk catalyst and/or corresponding bulk catalyst precursor mayfurther include an organic compound-based component, which may be basedon or derived from at least one organic complexing agent used in thepreparation of the bulk catalyst and/or corresponding bulk catalystprecursor. When an organic compound-based component is present, a molarratio of nickel in the composition to organic compound-based compositioncan be in a range of from 3:1 to 20:1.

The bulk catalyst and/or corresponding bulk catalyst precursor can havea BET specific surface area of at least 20 m²/g, at least 50 m²/g, atleast 75 m²/g, at least 100 m²/g. In any aspect, the self-supportedcatalyst and/or corresponding self-supported catalyst precursor can havea BET surface area of 250 m²/g or less, 200 m²/g or less, 175 m²/g orless, 150 m²/g or less, or 125 m²/g or less. Each of the above lowerlimits for the BET specific surface area is explicitly contemplated inconjunction with each of the above upper limits. The term “BET specificsurface area” refers to specific surface area as determined fromnitrogen adsorption data in accordance with the method of S. Brunauer,P. H. Emmett and E. Teller (J. Am. Chem. Soc. 1938, 60, 309-331).

The bulk catalyst and/or corresponding bulk catalyst precursor can havea pore volume of at least 0.02 cm³/g, at least 0.03 cm³/g, at least 0.04cm³/g, at least 0.05 cm³/g, at least 0.06 cm³/g, at least 0.08 cm³/g, atleast 0.09 cm³/g, at least 0.10 cm³/g, at least 0.11 cm³/g, at least0.12 cm³/g, at least 0.13 cm³/g, at least 0.14 cm³/g, at least 0.15cm³/g. In any aspect, the self-supported catalyst and/or correspondingself-supported catalyst precursor can have a pore volume of 0.80 cm³/gor less, 0.70 cm³/g or less, 60 cm³/g or less, 50 cm³/g or less 0.45cm³/g or less, 0.40 cm³/g or less, 0.35 cm³/g or less, 0.30 cm³/g orless. Each of the above lower limits for the pore volume is explicitlycontemplated in conjunction with each of the above upper limits. Porevolumes are determined from nitrogen adsorption data in accordance withthe procedures described by E. P. Barrett, L. G. Joyner and P. P.Halenda (J. Am. Chem. Soc. 1951, 73, 373-380).

The bulk catalyst and/or corresponding bulk catalyst precursor can havea particle density of at least 1.00 g/cm³ (e.g., at least 1.10 g/cm³, atleast 1.20 g/cm³, at least 1.30 g/cm³, at least 1.40 g/cm³, at least1.50 g/cm³, or at least 1.60 g/cm³). In any aspect, the self-supportedcatalyst and/or corresponding self-supported catalyst precursor can havea particle density of 3.00 g/cm³ or less (e.g., 2.90 g/cm³ or less, 2.80g/cm³ or less, 2.70 g/cm³ or less, 2.60 g/cm³ or less, 2.50 g/cm³ orless, or 2.40 g/cm³ or less, 2.30 g/cm³ or less, or 2.20 g/cm³ or less).Each of the above lower limits for the particle density is explicitlycontemplated in conjunction with each of the above upper limits.Particle density (D) is obtained by applying the formula D=M/V, where Mis the weight and V is the volume of the catalyst sample. The volume isdetermined by measuring volume displacement by submersing the sampleinto mercury under 28 mm Hg vacuum.

The bulk catalyst and/or corresponding bulk catalyst precursor may becharacterized via powder X-ray diffraction as a poorly crystallinematerial having broad diffraction peaks of low intensity. As usedherein, a broad diffraction peak means a peak having a full width athalf maximum (FWHM) of more than 1° (in 2-theta scale).

Preparation of the Bulk Catalysts and Catalyst Precursors

The present bulk catalyst precursor is a hydroxide and is prepared by amethod wherein the steps prior to sulfiding to form a bulk catalyst arecarried out a temperature of no more than 200° C. and wherein thecatalyst precursor remains a hydroxide prior to sulfiding to form a bulkcatalyst.

In one aspect, the first step in the preparation of the bulk catalystprecursor is a precipitation or co-gelation step, which involvesreacting in a reaction mixture a Ni-containing precursor compound insolution and molybdenum and tungsten precursor compounds in solution toobtain a precipitate or co-gel. The precipitation or co-gelation isperformed at a temperature and pH at which the nickel precursor and themolybdenum and tungsten precursors precipitate or form a co-gel.

Titanium can be introduced via either an in-situ or an ex-situ route. Inthe in-situ route, a Ti-containing precursor compound can be added tothe reaction mixture to precipitate titanium during co-precipitation orco-gelation of Ni—Mo—W oxides. In the ex-situ route, one or moretitanium precursor compounds can be composited with the precipitate orco-gel of Ni—Mo—W oxides.

In any aspect, in-situ addition of titanium can comprise: (a) combiningin a reaction mixture: (i) a Ni-containing precursor; (ii) aMo-containing precursor; (iii) a W-containing precursor; (iv) aTi-containing precursor; (v) optionally, an organic compound-basedcomponent; and (vi) a protic liquid; and (b) reacting the mixture underconditions sufficient to cause precipitation of the bulk catalystprecursor. The reaction mixture may be obtained by: (1) preparing afirst mixture comprising a Ni-containing precursor, a protic liquid,and, optionally, an organic compound-based component; (2) preparing asecond mixture comprising a Mo-containing precursor, a W-containingprecursor, and a protic liquid; (3) adding a Ti-containing precursor tothe first mixture, the second mixture, or a combination thereof; (4)heating both the first and second mixtures to a temperature of from 60°C. to 150° C.; (5) combining the first and second mixtures together.After the reaction step, if necessary, the obtained bulk catalystprecursor can be separated from the liquid, e.g., via filtration orspray drying.

In any aspect, ex-situ addition of titanium can comprise: (a) combiningin a reaction mixture: (i) a Ni-containing precursor; (ii) aMo-containing precursor; (iii) a W-containing precursor; (iv)optionally, an organic compound-based component; and (v) a proticliquid; and (b) reacting the mixture under conditions sufficient tocause precipitation of an intermediate bulk catalyst precursor; and (c)compositing the intermediate bulk catalyst precursor with aTi-containing precursor to form the bulk catalyst precursor. Thereaction mixture may be obtained by: (1) preparing a first mixturecomprising a Ni-containing precursor, a protic liquid, and, optionally,an organic compound-based component; (2) preparing a second mixturecomprising a Mo-containing precursor, a W-containing precursor, and aprotic liquid; (3) heating both the first and second mixtures to atemperature of from 60° C. to 150° C.; and (4) combining the first andsecond mixtures together. After the reaction step, if necessary, theobtained intermediate bulk catalyst can be separated from the liquid,e.g., via filtration or spray drying.

The temperature at which the catalyst precursor is formed can be in arange of from 60° C. to 150° C. If the temperature is below the boilingpoint of the protic liquid, such as 100° C. in the case of water, theprocess is generally carried out at atmospheric pressure. The reactioncan also be performed under hydrothermal conditions wherein the reactiontemperature is above the boiling temperature of the protic liquid.Typically, such conditions give rise to a pressure above atmosphericpressure and then the reaction is preferably performed in an autoclave,preferably under autogenous pressure, that is without applyingadditional pressure. An autoclave is a device capable of withstandingpressure designed to heat liquids above their boiling temperature. Inany aspect, the bulk catalyst precursor formation process is carried outat one or more temperatures either (a) in a range of 50° C. to 100° C.under atmospheric pressure or (b) above 100° C. under autogenouspressure.

The reaction time, both under atmospheric and hydrothermal reactionconditions, is chosen sufficiently long to substantially complete thereaction. The reaction times can be very short (e.g., shorter than 1hour with highly reactive reactants). Clearly, longer reaction times,perhaps as long as 24 hours, may be required for raw materials with lowreactivity. The reaction time can in some circumstances vary inverselywith temperature.

Generally, the reaction mixture is kept at its natural pH during thereaction step. The pH can be maintained in a range of 0 to 12 (e.g., 3to 9, or 5 to 8). The pH can be changed to increase or decrease the rateof precipitation or co-gelation, depending on the desiredcharacteristics of the product.

The metal precursors can be added to the reaction mixture in solution,suspension or a combination thereof. If soluble salts are added as such,they will dissolve in the reaction mixture and subsequently beprecipitated or co-gelled.

Representative examples of Mo-containing precursor compounds includemolybdenum (di and tri) oxide, molybdic acid, alkali metal molybdates(e.g., sodium molybdate, potassium molybdate), ammonium molybdates(e.g., ammonium molybdate, ammonium dimolybdate, ammoniumheptamolybdate), and heteropolymolybdates (e.g., silicomolybdic acid,phosphomolybdic acid).

Representative examples of W-containing precursor compounds includetungsten (di and tri) oxide, tungstic acid, alkali metal tungstates(e.g., sodium tungstate, potassium tungstate, sodium metatungstate,sodium polytungstate), ammonium tungstates (e.g., ammonium tungstate,ammonium metatungstate, ammonium paratungstate), andheteropolytungstates (e.g., silicotungstic acid, phosphotungstic acid).

Representative examples of Ni-containing precursor compounds includenickel acetate, nickel acetylacetonate, nickel bromide, nickelcarbonate, nickel hydroxycarbonate, nickel bicarbonate, nickel chloride,nickel nitrate, nickel phosphate, and nickel sulfate.

Any titanium-containing compound suitable for the preparation of a bulkcatalyst of the type described herein may be used as a Ti-containingprecursor compound. The Ti-containing precursor can comprise atetravalent titanium (Ti⁴⁺)-containing compound, a trivalent titanium(Ti³⁺)-containing compound, or a combination thereof.

Representative Ti-containing precursor compounds include TiO₂nanoparticles, colloidal TiO₂, fumed TiO₂, titanium hydroxide,organotitanium compounds, titanium halides, and water-soluble titaniumsalts.

The titanium dioxide nanoparticles may be any type of titanium dioxide.The titanium dioxide can have a high content of anatase and/or rutile.For example, the titanium dioxide may comprise at least 50, 55, 60, 65,70, 75, 80, 85, 90, 95, 98, or even at least 99 percent by weight ofanatase and/or rutile. In some embodiments, the titanium dioxideconsists essentially of anatase and/or rutile. The titanium dioxideparticles preferably have a median particle size (D50) of less than 100nm (e.g., 3 to 50 nm). The titanium oxide nanoparticles may beintroduced in the composition as a sol prepared by dispersion in adispersant, as a water- or solvent-containing paste, or as a powder.Examples of the dispersant used to prepare a sol include water, alcohols(e.g., methanol, ethanol, isopropanol, n-butanol, isobutanol), andketones (e.g., methyl ethyl ketone, methyl isobutyl ketone).

Representative organotitanium compounds include titanium alkoxides ofthe general structure Ti(OR)₄ where each R is independently C1 to C4alkyl and titanium acyl compounds. Representative titanium alkoxidesinclude titanium tetramethoxide, titanium tetraethoxide, titaniumtetrapropoxide, titanium tetraisopropoxide, titanium tetra-n-butoxideand titanium tetra-tert-butoxide. Representative titanium acyl compoundsinclude titanium acetylacetonate, titanium oxyacetylacetonate, andtitanium acetate. Other representative organotitanium compounds includethose characterized by the general formula Ti(OR′)₂(acac)₂ wherein eachR′ is independently C1 to C4 alkyl and “acac” is acetylacetonate.

Titanium halides represented by the formula TiX₄ or TiX₃, where X ischloro, bromo, iodo or fluoro, or mixtures thereof, may be used astitanium precursors. In an aspect, the titanium halide is titaniumtetrachloride, titanium tetrabromide, or a combination thereof.

The present disclosure also contemplates the use of organotitaniumhalides such as chlorotitanium triisopropoxide [Ti(O-i-Pr)₃Cl] and thelike as Ti-containing precursor compounds.

Representative water-soluble titanium salts include titanium nitrate andtitanium sulfate.

The organic compound-based component can be an organic compound suitablefor forming metal-ligand complexes in solution. The organiccompound-based component may be selected from an organic acid or saltthereof, a sugar, a sugar alcohol, or a combination thereof.

Representative organic acids include glyoxylic acid, pyruvic acid,lactic acid, malonic acid, oxaloacetic acid, malic acid, fumaric acid,maleic acid, tartaric acid, gluconic acid, citric acid, oxamic acid,serine, aspartic acid, glutamic acid, iminodiacetic acid,ethylenediaminetetraacetic acid, and the like.

Representative sugars include fructose, glucose, galactose, mannose,sucrose, lactose, maltose, and the like, and derivatives thereof.

Representative sugar alcohols include erythritol, xylitol, mannitol,sorbitol, and the like, and derivatives thereof.

The protic liquid can be any protic liquid which does not interfere withthe reactions of the metal compounds. Examples include water, carboxylicacids, and alcohols (e.g., methanol, ethanol, ethylene glycol). Theprotic liquid can be water alone or a mixture of water and an alcohol.

Additional Processing

The bulk catalyst precursor may be subjected to one or more of thefollowing process steps before being used in hydroprocessing processes:(i) compositing with a material selected from the group of bindermaterials, conventional hydroprocessing catalysts, cracking compounds,or mixtures thereof; (ii) spray-drying, (flash) drying, milling,kneading, slurry-mixing, dry or wet mixing, or combinations thereof;(iii) shaping; (iv) drying and/or thermally treating; and (v) sulfiding.The listing of these process steps as (i) to (v) is for convenienceonly; it is not a statement that these processes are constrained to beperformed in this order. These process steps will be explained in moredetail below.

Additional Process Step (i)—Compositing with Further Materials

If so desired, an additional material selected from the group of bindermaterials, conventional hydroprocessing catalysts, cracking compounds,or mixtures thereof can be added during the above-described preparationof the bulk catalyst precursor or the bulk catalyst precursor after itspreparation. Preferably, the material is added subsequent to thepreparation of the bulk catalyst precursor and prior to spray-drying orany alternative technique, or, if spray-drying or the alternativetechniques are not applied, prior to shaping. Optionally, the bulk metalprecursor prepared as described above can be subjected to a solid-liquidseparation before being composited with the material. After solid-liquidseparation, optionally, a washing step can be included. Further, it ispossible to thermally treat the bulk catalyst particles after anoptional solid-liquid separation and drying step and prior to its beingcomposited with the material.

In all the above-described process alternatives, the phrase “compositingthe bulk catalyst precursor with a material” means that the material isadded to the bulk metal particles or vice versa and the resultingcomposition is mixed. Mixing is preferably done in the presence of aliquid (“wet mixing”). This improves the mechanical strength of thefinal bulk catalyst composition.

Compositing the bulk catalyst precursor with the additional materialand/or incorporating the material during the preparation of the catalystprecursor leads to bulk catalyst of particularly high mechanicalstrength, in particular if the median particle size of the bulk metalparticles is in the range of at least 0.5 μm (e.g., at least 1 μm, atleast about 2 μm) but not more than 5000 μm (e.g., not more than 1000μm, not more than 500 μm, not more than 150 μm). The median particlediameter of the catalyst precursor can be in a range of 1 to 150 μm(e.g., 2 to 150 μm).

The compositing of the bulk metal particles with the material results inbulk metal particles embedded in this material or vice versa. Normally,the morphology of the bulk metal particles is essentially maintained inthe resulting bulk catalyst composition.

The binder materials to be applied may be any materials conventionallyapplied as binders in hydroprocessing catalysts. Examples are silica,silica-alumina (e.g., conventional silica-alumina, silica-coated aluminaand alumina-coated silica), alumina (e.g., boehmite, pseudoboehmite, orgibbsite), titania, titania-coated alumina, zirconia, hydrotalcite, ormixtures thereof. Preferred binders are silica, silica-alumina, alumina,titania, titania-coated alumina, zirconia, bentonite, or mixturesthereof. These binders may be applied as such or after peptization.

If alumina is used as binder, the surface area of the alumina can be ina range of 50 to 600 m²/g (e.g., 100 to 450 m²/g), as measured by theBET method. The pore volume of the alumina can be in a range of 0.1 to1.5 cm³/g, as measured by nitrogen adsorption.

Generally, the binder material to be added has less catalytic activitythan the bulk metal particles or no catalytic activity at all. Binderamounts from 0 to 40 wt. % of the total composition can be suitable,depending on the envisaged catalytic application. However, to takeadvantage of the resulting high activity of the bulk metal particles ofthe present disclosure, the binder amounts to be added generally are ina range of 0.1 to 30 wt. % (e.g., 1 to 20 wt. %, 3 to 20 wt. %, or 4 to12 wt. %) of the total composition.

Additional Process Step (ii)—Spray-Drying, (Flash) Drying, Milling,Kneading, Slurry Mixing, Dry or Wet Mixing

The bulk catalyst precursor optionally comprising any of the above(further) materials can be subjected to spray-drying, (flash) drying,milling, kneading, slurry-mixing, dry or wet mixing, or combinationsthereof, with a combination of wet mixing and kneading or slurry mixingand spray-drying being preferred.

These techniques can be applied either before or after any of the above(further) materials are added (if at all), after solid-liquidseparation, before or after a thermal treatment, and subsequent tore-wetting.

Preferably, the catalyst precursor is both composited with any of theabove materials and subjected to any of the above techniques. It isbelieved that by applying any of the above-described techniques ofspray-drying, (flash) drying, milling, kneading, slurry-mixing, dry orwet mixing, or combinations thereof, the degree of mixing between thecatalyst precursor particles and any of the above materials is improved.This applies to cases where the material is added before as well asafter the application of any of the above-described methods. However, itis generally preferred to add the material prior to step (ii). If thematerial is added subsequent to step (ii), the resulting composition canbe thoroughly mixed by any conventional technique prior to any furtherprocess steps such as shaping. An advantage of spray-drying is that nowaste-water streams are obtained when this technique is applied.

Spray-drying can be carried out at an outlet temperature in the range of100° to 200° C. (e.g., 120° to 180° C.).

Dry mixing means mixing the catalyst precursor particles in the drystate with any of the above materials in the dry state. Wet mixinggenerally comprises mixing the wet filter cake comprising the catalystprecursor particles and optionally any of the above materials as powdersor wet filter cake to form a homogenous paste thereof.

Additional Process Step (iii)—Shaping

If so desired, the bulk catalyst precursor optionally comprising any ofthe above (further) materials may be shaped optionally after step (ii)having been applied. Shaping comprises extrusion, pelletizing, beadingand/or spray-drying. It is noted that if the bulk catalyst compositionis to be applied in slurry-type reactors, fluidized beds, moving beds,or expanded beds, generally spray-drying or beading is applied. Forfixed-bed or ebullating bed applications, generally the bulk catalystcomposition is extruded, pelletized and/or beaded. In the latter case,at any stage prior to or during the shaping step, any additives whichare conventionally used to facilitate shaping can be added. Theseadditives may comprise aluminum stearate, surfactants, graphite, starch,methyl cellulose, bentonite, polyethylene glycols, polyethylene oxides,or mixtures thereof. Further, when alumina is used as binder, it may bedesirable to add acids such as nitric acid prior to the shaping step topeptize the alumina and to increase the mechanical strength of theextrudates.

If the shaping comprises extrusion, beading and/or spray-drying, it ispreferred that the shaping step is carried out in the presence of aliquid, such as water. For extrusion and/or beading, the amount ofliquid in the shaping mixture, expressed as loss-on-ignition, can be ina range of 20% to 80%.

Additional Process Step (iv)—Drying and/or Thermally Treating

After an optional drying step, preferably above 100° C., the resultingshaped bulk catalyst composition may be thermally treated, if desired. Athermal treatment, however, is not essential to the process of thisdisclosure. A “thermal treatment” according to the present disclosurerefers to a treatment performed at a temperature of from 100° C. to 200°C. for a time varying from 0.5 to 48 hours in an inert gas such asnitrogen, or in an oxygen-containing gas, such as air or pure oxygen.The thermal treatment can be carried out in the presence of water steam.

In all the above process steps the amount of liquid must be controlled.Where, prior to subjecting the bulk catalyst composition tospray-drying, the amount of liquid is too low, additional liquid must beadded. Conversely where, prior to extrusion of the bulk catalystcomposition, the amount of liquid is too high, the amount of liquid mustbe reduced using solid-liquid separation techniques such as filtration,decantation, or evaporation and, if necessary, the resulting materialcan be dried and subsequently re-wetted to a certain extent. For all theabove process steps, it is within the scope of the skilled person tocontrol the amount of liquid appropriately.

Additional Process Step (v)—Sulfiding

The tetrametallic bulk catalyst is generally used in its sulfided form.Catalyst sulfiding can be carried out in any way effective for makingthe catalyst in sulfide form, including conventional sulfiding methods.Sulfidation can be carried out by contacting the catalyst precursor,directly after its preparation or after any one of additional processsteps (i)-(iv), with a sulfur-containing compound such as elementalsulfur, hydrogen sulfide, dimethyl disulfide, or organic or inorganicpolysulfides. The sulfidation step can be carried out in the liquid andthe gaseous phase.

The sulfidation can generally be carried out in-situ and/or ex-situ.Preferably, the sulfidation is carried out in-situ (i.e., thesulfidation is carried out in the hydroprocessing reactor subsequent tothe bulk catalyst precursor composition being loaded into thehydroprocessing unit).

Use in Hydroprocessing

The bulk catalyst precursor of the present disclosure is particularlyuseful for hydroprocessing hydrocarbon feedstocks. Hydroprocessingincludes processes such as hydrodesulfurization, hydrodenitrogenation,hydrodemetallation, hydrodearomatization, hydrogenation, hydrogenolysis,hydrotreating, hydroisomerizaiton, and hydrocracking.

A wide range of petroleum and chemical hydrocarbon feedstocks can behydroprocessed in accordance with the present disclosure. Hydrocarbonfeedstocks include those obtained or derived from crude petroleum oil,from tar sands, from coal liquefaction, from shale oil and fromhydrocarbon synthesis, such as reduced crudes, hydrocrackates,raffinates, hydrotreated oils, atmospheric and vacuum gas oils, cokergas oils, atmospheric and vacuum residua, deasphalted oils, dewaxedoils, slack waxes, Fischer-Tropsch waxes, biorenewable feedstocks, andmixtures thereof. Suitable feedstocks range from relatively lightdistillate fractions up to heavy feedstocks, such as gas oils, lube oilsand residua. Examples of light distillate feedstocks include naphtha(typical boiling range of from about 25° C. to about 210° C.), diesel(typical boiling range of from about 150° C. to about 400° C.), keroseneor jet fuel (typical boiling range of from about 150° C. to about 250°C.) and the like. Examples of heavy feedstocks include vacuum (or heavy)gas oils (typical boiling range of from about 315° C. to about 610° C.),raffinates, lube oils, cycle oils, waxy oils and the like. Preferredhydrocarbon feedstocks have a boiling range of from about 150° C. toabout 650° C. (e.g., from about 150° C. to about 450° C.).

Hydroprocessing conditions can include a temperature of from 200° C. to450° C., or from 315° C. to 425° C.; a pressure of from 250 to 5000 psig(1.7 to 34.6 MPa), or from 300 to 3000 psig (2.1 to 20.7 MPa); a liquidhourly space velocity (LHSV) of from 0.1 to 10 h⁻¹, or from 0.5 to 5h⁻¹; and a hydrogen gas rate of from 100 to 15,000 SCF/B (17.8 to 2672m³/m³), or from 500 to 10,000 SCF/B (89 to 1781 m³/m³).

Hydroprocessing according to the present disclosure can be practiced inone or more reaction zones using any suitable reactor system such as oneor more fixed-bed, moving-bed or fluidized bed reactors. A fixed bedreactor can include one or more vessels, single or multiple beds ofcatalyst in each vessel, and various combinations of hydroprocessingcatalyst in one or more vessels.

EXAMPLES

The following illustrative examples are intended to be non-limiting.

Example 1 (Comparative) Synthesis of Bulk Catalyst Precursor[Ni(2)-Mo(1)-W(1)]

Preparation of Solution A: 70.6 g of ammonium heptamolybdate and 102.0 gof ammonium metatungstate hydrate were added into 2000 g of deionizedwater in a 4 L flask. The pH was adjusted to 9.8 with ammonia water. Thesolution was then heated to 80° C.

Preparation of Solution B: In a separate 500 mL beaker, 232.6 g ofnickel nitrate and 13.9 of maleic acid were dissolved into 100 g ofdeionized water.

Solution B was added into Solution A at a rate of 10 mL/min. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours.

The slurry was filtered, and the wet cake collected. The wet cake waswashed with 300 g of deionized water to remove ammonium nitrateby-product. The wet cake was then dried in an oven at 130° C. to removeany moisture.

Example 2 (Comparative) Synthesis of Bulk Catalyst Precursor[Ni—Mo—W—Co]

Preparation of Solution A: 45.0 g of ammonium heptamolybdate and 58.0 gof ammonium metatungstate were added into 2500 g of deionized water in a4 L flask. The pH was adjusted to 9.8 with ammonia water. The solutionwas then heated to 80° C.

Preparation of Solution B: In a separate 500 mL beaker, 140.0 g ofnickel nitrate, 140.0 of cobalt nitrate, and 16.0 g of maleic acid weredissolved into 125 g of deionized water.

Solution B was added into Solution A at a rate of 10 mL/min. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours.

The slurry was filtered, and the wet cake collected. The wet cake waswashed with 300 g of deionized water to remove ammonium nitrateby-product. The wet cake was then dried in an oven at 130° C. to removeany moisture.

Example 3 Synthesis of Bulk Catalyst Precursor [Ni—Mo—W—Ti] with Ex-SituAddition of Ti

Preparation of Solution A: 10.4 g of ammonium heptamolybdate and 44.8 gof ammonium metatungstate were added into 1000 g of deionized water in a4 L flask. The pH was adjusted to 9.8 with ammonia water. The solutionwas then heated to 80° C.

Preparation of Solution B: In a separate 500 mL beaker, 128.5 g ofnickel nitrate and 7.1 g of maleic acid were dissolved into 100 g ofdeionized water.

Solution B was added into Solution A at a rate of 10 mL/min. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours.

The slurry was filtered, and the wet cake collected. The wet cake waswashed with 300 g of deionized water to remove ammonium nitrateby-product. The wet cake was transferred into a beaker and heated at 60°C. with stirring. Then, 100 g of hydrophilic fumed TiO₂ (AEROXIDE® TiO₂P25, Evonik) was mixed into the wet cake until the mixture washomogeneous. The wet cake was dried at 130° C. to remove any moisture.

Example 4 Synthesis of Bulk Catalyst Precursor [Ni—Mo—W—Ti] with In-SituAddition of Ti

Preparation of Solution A: 10.4 g of ammonium heptamolybdate 44.8 g ofammonium metatungstate were added into 1000 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water. The solution wasthen heated to 80° C.

Preparation of Gel C: In a 500 mL beaker, 128.3 g of nickel nitrate wasdissolved in 210 g of ethylene glycol. In a separate 1 L beaker, 116.1 gof titanium tetra-n-butoxide [Ti(OBu)₄] was mixed into 1200 g ofethylene glycol. The Ti(OBu)₄/ethylene glycol solution was added to thenickel nitrate/ethylene glycol solution at a rate of 5 mL/min. Gel C wasaged at 80° C. for 2 hours.

Gel C was then added into Solution A at a rate of 10 mL/min. The pH wasmonitored during addition. Green precipitates formed upon addition ofGel C. The final pH was at 6.0-7.0 after addition. The slurry was agedat 80° C. for 4 hours.

The slurry was filtered, and the wet cake collected. The wet cake waswashed with 300 g of deionized water to remove ammonium nitrateby-product and ethylene glycol. The wet cake was dried at 130° C. toremove any moisture.

FIG. 3 shows the isotherm plot of N₂ physisorption conducted at 77 K onthe catalyst precursor. FIG. 3 indicates that this material has type Bslit-shaped porosity.

FIG. 4 displays HAADF-STEM images obtained for the catalyst precursor.FIG. 4 indicates that all four metal oxides are homogeneouslydistributed. No islands of TiO₂ are observed.

Example 5 Synthesis of Bulk Catalyst Precursor [Ni—Mo—W—Ti] with In-SituAddition of Ti

Example 4 was repeated except that 766.1 g of titanium tetra-n-butoxidewas used.

FIG. 5 shows the isotherm plot of N₂ physisorption conducted at 77 K onthe catalyst precursor. FIG. 5 indicates that this material has a type Bslit-shaped porosity.

Example 6 Production of Extrudates

Prior to catalytic evaluation, catalyst precursors were shaped intoextrudates. Dried catalyst precursor was ground to a fine powder (<100mesh) and mixed with a proper amount of a binder and water to make anextrudable mixture, followed by extrusion on a Carver press.

Example 7 Bulk Catalyst Precursor Characterization

The particle density (D), BET surface area (SA) and pore volume (PV)were measured for the bulk catalyst precursors of Examples 1-5. Theresults are shown in Table 1 below. Table 1 shows addition of TiO₂ canimprove pore volume and decrease particle density.

TABLE 1 D N₂ BET SA N₂ PV Precursor Composition [g/cm³] [m²/g] [cm³/g]Example 1 Ni—Mo—W 2.45 124 0.09 Example 2 Ni—Mo—W—Co 2.47 136 0.09Example 3 Ni—Mo—W—Ti 1.94 118 0.11 Example 4 Ni—Mo—W—Ti 1.67 164 0.20Example 5 Ni—Mo—W—Ti 2.14 159 0.23

Example 8 Catalyst Evaluation—Hydrogenolysis of Tetralin

Catalyst precursor extrudates from Examples 1 and 3-4 were tested fortetralin hydrogenolysis activity in a fixed bed reactor. All catalystprecursors were pre-sulfided using tetralin spiked with 300 wppm ofsulfur in the form of dimethyl disulfide. The catalyst precursors weresulfided using the spiked tetralin feed at 450° F. and 800 psig H₂pressure for 24 hours and then ramped to 650° F. at 25° F./hour and heldat 650° F./800 psig for 10 hours.

The catalyst was evaluated at a reactor total pressure of 2300 psig, ahydrogen feed rate of 8000 SCF/B, and a LHSV of 1 h⁻¹. The tetralin feedcontained 300 wppm sulfur.

Table 2 shows the hydrogenolysis performance of each catalyst.

TABLE 2 Yield of Ring-Opening Products (%) Example 1 Example 3 Example 4Temp. [Ni—Mo— [Ni—Mo— [Ni—Mo— [° F.] W] W—Ti] W—Ti] TiO₂ ^((a)) 620 0.40.4 0.3 0.1 640 1.2 1.3 1.5 0.4 660 3.6 3.9 3.7 0.2 680 8.8 8.0 9.3 0.2700 16.0 17.2 18.5 0.2 720 26.0 27.6 34.9 0.4 740 37.6 40.0 50.2 0.7^((a))Hydrophilic fumed TiO₂ (AEROXIDE ® TiO₂ P 25, Evonik).

The results show that the activity of the bulk catalyst of Example 3 iscomparable to the conventional bulk catalyst of Example 1, although thebulk catalyst has a lesser amount of active metals (i.e., Ni, Mo and W).The activity of the bulk catalyst of Example 4 is significantly higherthan the bulk catalysts of Examples 1 and 3, at higher temperatures.Without being bound by any theory, it is believed that the in-situ routeto introduce TiO₂ leads to higher dispersion of metals and increasesacidity of the catalyst considerably. The TiO₂ control catalyst itselfdoes not have sufficient activity to open rings in any substantialamount.

Example 9 (Comparative) Synthesis of Bulk Catalyst Precursor[Ni(2.5)-Mo(1)-W(1.1)]

Preparation of Solution A: 45 g of ammonium heptamolybdate and 72 g ofammonium metatungstate were added into 2000 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water and the solutionheated up to 80° C.

Preparation of Solution B: 184.5 g of nickel nitrate and 10.1 g ofmaleic acid were dissolved into 100 g of deionized water.

Solution B was added into Solution A within 15 minutes. Greenprecipitates were formed during the addition of Solution B. The final pHwas at 6.0-7.0. The slurry was aged with stirring at 80° C. for 4 hours.After ageing, the product was recovered by filtration, washed withdeionized water and dried at 130° C.

Example 10 (Comparative) Synthesis of Bulk Catalyst Precursor[Ni(7.5)-Mo(1)-W(3)]

Example 9 was repeated, except that the following reagents were used inthe amounts indicated in parentheses: ammonium heptamolybdate (10.4 g),ammonium metatungstate (44.8 g), maleic acid (5.8 g) and nickel nitrate(128.3 g).

Example 11 (Comparative) Synthesis of Bulk Catalyst Precursor[Ni(3.8)-Mo(1)-W(1.1)]

Example 9 was repeated, except that the following reagents were used inthe amounts indicated in parentheses: ammonium molybdate (17.6 g),ammonium heptamolybdate (27.8 g), maleic acid (5.8 g) and nickel nitrate(110.3 g).

Example 12 Synthesis of Bulk Catalyst Precursor[Ni(2.5)-Mo(1)-W(1.1)-Ti(2.7)] with In-Situ Addition of Ti

Preparation of Slurry A: 45 g of ammonium heptamolybdate, 72 g ofammonium metatungstate and 56 g of TiO₂ (Venator Hombikat 8602) wereadded into 2000 g of deionized water in a 4 L flask. The pH was adjustedto 9.8 with ammonia water and the solution heated up to 80° C.

Preparation of Solution B: 184.5 g of nickel nitrate and 10.1 g ofmaleic acid were dissolved into 100 g of deionized water.

Solution B was added into Slurry A within 15 minutes. Green precipitateswere formed during the addition of Solution B. The final pH was at6.0-7.0. The slurry was aged with stirring at 80° C. for 4 hours. Afterageing, the product was recovered by filtration, washed with deionizedwater and dried at 130° C.

Example 13 Synthesis of Bulk Catalyst Precursor[Ni(2.5)-Mo(1)-W(1.1)-Ti(2.7)] with Ex-Situ Addition of Ti

Preparation of Solution A: 45 g of ammonium heptamolybdate and 72 g ofammonium metatungstate were added into 2000 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water and the solutionheated up to 80° C.

Preparation of Solution B: 184.5 g of nickel nitrate and 10.1 g ofmaleic acid were dissolved into 100 g of deionized water.

Solution B was added into Solution A within 15 minutes. Greenprecipitates were formed during the addition of Solution B. The final pHwas at 6.0-7.0. The slurry was aged with stirring at 80° C. for 4 hours.After ageing, the product was recovered by filtration. The filter cakeand 56 g of TiO₂ (Venator Hombikat 8602) were mixed to homogeneity andstirred at 80° C. for 2 hours. The mixture was recovered by filtration,washed with deionized water and dried at 130° C.

Example 14 Synthesis of Bulk Catalyst Precursor[Ni(2.5)-Mo(1)-W(1.1)-Ti(2.7)]

Example 12 was repeated except that Venator Hombikat ADW-1 TiO₂ was usedas the source of TiO₂.

Example 15 Synthesis of Bulk Catalyst Precursor[Ni(6.6)-Mo(1)-W(3)-Ti(9.8)] with Ex-Situ Addition of Ti

Preparation of Solution A: 32 g of ammonium heptamolybdate and 139.4 gof ammonium metatungstate were added into 2000 g of deionized water in a4 L flask. The pH was adjusted to 9.8 with ammonia water and thesolution heated up to 80° C.

Preparation of Solution B: 354.7 g of nickel nitrate and 10.1 g ofmaleic acid were dissolved into 100 g of deionized water.

Solution B was added into Solution A within 15 minutes. Greenprecipitates were formed during the addition of Solution B. The final pHwas at 6.0-7.0. The slurry was aged with stirring at 80° C. for 4 hours.After ageing, the product was recovered by filtration. The filter cakeand 56 g of TiO₂ (Evonik AEROXIDE® E0167) were mixed to homogeneity andstirred at 80° C. for 2 hours. The mixture was recovered by filtration,washed with deionized water and dried at 130° C.

Example 16 Synthesis of Bulk Catalyst Precursor[Ni(6.6)-Mo(1)-W(3)-Ti(5)]

Example 14 was repeated except that 93.1 of TiO₂ (Evonik AEROXIDE®E0167) was used.

Example 17 Synthesis of Bulk Catalyst Precursor[Ni(6.6)-Mo(1)-W(3)-Ti(2.5)]

Example 14 was repeated except that 46.6 of TiO₂ (Evonik AEROXIDE®E0167) was used.

Example 18 Synthesis of Bulk Catalyst Precursor[Ni(2.5)-Mo(1)-W(1.1)-Ti(3)] with In-Situ Addition of Ti Compound

Preparation of Solution A: 45 g of ammonium heptamolybdate and 72 g ofammonium metatungstate were added into 2000 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water and the solutionheated up to 80° C.

Preparation of Gel C: 184.3 g of nickel nitrate was dissolved in 210 gof ethylene glycol. In a separate 1 L beaker, 321.6 g of Ti(OBu)₄ wasmixed into 1200 g of ethylene glycol. The Ti(OBu)₄ mixture was thenadded to the Nickel nitrate mixture at a rate of 5 mL/min with vigorousmixing. The resulting gel was aged at 80° C. for 2 hours.

Gel C was added into solution A within 15 minutes. Green precipitateswere formed during the addition of gel C. The final pH was at 6.0-7.0.The slurry was aged with stirring at 80° C. for 4 hours. After ageing,the product was recovered by filtration, washed with deionized water anddried at 130° C.

Example 19 Synthesis of Bulk Catalyst Precursor[Ni(7.5)-Mo(1)-W(3)-Ti(3.8)]

Example 16 was repeated except that 128.3 g of nickel nitrate wasdissolved in 210 g of ethylene glycol and that 76.1 g of Ti(OBu)₄ wasmixed into 230 g of ethylene glycol.

Example 20 Synthesis of Bulk Catalyst Precursor[Ni(2.5)-Mo(1)-W(1.1)-Ti(2.7)]

Example 12 was repeated except that anatase nanopowder (99.5% 5 nm) fromU.S. Research Nanomaterials, Inc. was used as the source of TiO₂.

Example 21 Synthesis of Bulk Catalyst Precursor[Ni(7.5)-Mo(1)-W(3)-Ti(21.2)] with Ex-Situ Addition of Ti

Preparation of Solution A: 10.4 g of ammonium heptamolybdate and 44.8 gof ammonium metatungstate were added into 1000 g of deionized water in a4 L flask. The pH was adjusted to 9.8 with ammonia water and thesolution heated up to 80° C.

Preparation of Solution B: 128.5 g of nickel nitrate and 7.1 g of maleicacid were dissolved into 100 g of deionized water.

Solution B was added into Solution A within 15 minutes. Greenprecipitates were formed during the addition of Solution B. The final pHwas at 6.0-7.0. The slurry was aged with stirring at 80° C. for 4 hours.After ageing, the product was recovered by filtration. The filter cakeand 100 g of hydrophilic fumed TiO₂ (Evonik AEROXIDE® P 25) were mixedto homogeneity and stirred at 80° C. for 2 hours. The mixture wasrecovered by filtration, washed with deionized water and dried at 130°C.

Example 22 Synthesis of Bulk Catalyst Precursor[Ni(2.5)-Mo(1)-W(1.1)-Ti(2.7)]

Example 12 was repeated except that Venator Hombikat S141 was used asthe source of TiO₂.

Example 23 Synthesis of Bulk Catalyst Precursor[Ni(2.5)-Mo(1)-W(1.1)-Ti(6.2)]

Example 12 was repeated except that Venator S141 was used as the sourceof TiO₂ and in an amount of 128 g.

Example 24 Synthesis of Bulk Catalyst Precursor[Ni(2.5)-Mo(1)-W(1.1)-Ti(2.7)] with In-Situ Addition of Ti

Preparation of Slurry A: 56 g of ammonium heptamolybdate, 90 g ofammonium metatungstate and 467 g of colloidal TiO₂ (15 wt. % TiO₂solids, Cerion Nanomaterials) were added into 2000 g of deionized waterin a 4 L flask. The pH was adjusted to 9.8 with ammonia water and thesolution heated up to 80° C.

Preparation of Solution B: 230 g of nickel nitrate and 10.1 g of maleicacid were dissolved into 100 g of deionized water.

Solution B was added into Slurry A within 15 minutes. Green precipitateswere formed during the addition of Solution B. The final pH was at6.0-7.0. The slurry was aged with stirring at 80° C. for 4 hours. Afterageing, the product was recovered by filtration, washed with deionizedwater and dried at 130° C.

Example 25 (Comparative) Synthesis of Bulk Catalyst Precursor[Ni(7.5)-Mo(1)-W(3)-Si(2)] with Ex-Situ Addition of Silicon

Preparation of Solution A: 10.4 g of ammonium heptamolybdate and 44.8 gof ammonium tungstate were added into 1000 g of deionized water in a 4 Lflask. The pH was adjusted to 9.8 with ammonia water and the solutionheated up to 80° C.

Preparation of Solution B: 128.5 g of nickel nitrate and 7.1 g of maleicacid were dissolved into 100 g of deionized water.

Solution B was added into Solution A within 15 minutes. Greenprecipitates were formed during the addition of Solution B. The final pHwas at 6.0-7.0. The slurry was aged with stirring at 80° C. for 4 hours.After ageing, the product was recovered by filtration. The filter cakeand 8.9 g of tetraethyl orthosilicate (TEOS) were mixed to homogeneityand stirred at 80° C. for 2 hours. The mixture was recovered byfiltration, washed with deionized water and dried at 130° C.

Example 26 (Comparative) Bulk Catalyst Precursor[Ni(6.6)-Mo(1)-W(3)-Si(6.6)] with Ex-Situ Addition of Silicon

Preparation of Solution A: 32.4 g of ammonium heptamolybdate and 139.4 gof ammonium tungstate were added into 2000 g of deionized water in a 4 Lflask. The pH was adjusted to 9.8 with ammonia water and the solutionheated up to 80° C.

Preparation of Solution B: 354.7 g of nickel nitrate and 10.1 g ofmaleic acid were dissolved into 100 g of deionized water.

Solution B was added into Solution A within 15 minutes. Greenprecipitates were formed during the addition of Solution B. The final pHwas at 6.0-7.0. The slurry was aged with stirring at 80° C. for 4 hours.After ageing, the product was recovered by filtration. The filter cakeand 91 g of silica gel (Davisil Grade 636) were mixed to homogeneity andstirred at 80° C. for 2 hours. The mixture was recovered by filtration,washed with deionized water and dried at 130° C.

Example 27 (Comparative) Synthesis of Bulk Catalyst Precursor[Ni(6.6)-Mo(1)-W(3)-Si(2.9)]

Example 27 was repeated except that 39 g of the silica gel was used.

Example 28 (Comparative) Synthesis Bulk Catalyst Precursor[Ni(2.5)-Mo(1)-W(1.1)-Zr(1.8)] with Ex-Situ Addition of Zirconium

Preparation of Solution A: 45 g of ammonium heptamolybdate and 72 g ofammonium tungstate were added into 2000 g of deionized water in a 4 Lflask. The pH was adjusted to 9.8 with ammonia water and the solutionheated up to 80° C.

Preparation of Solution B: 184.5 g of nickel nitrate and 10.1 g ofmaleic acid were dissolved into 100 g of deionized water.

Solution B was added into Solution A within 15 minutes. Greenprecipitates were formed during the addition of Solution B. The final pHwas at 6.0-7.0. The slurry was aged with stirring at 80° C. for 4 hours.After ageing, the product was recovered by filtration. The filter cakeand 56 g of calcined ZrO₂ (Aldrich) were mixed to homogeneity andstirred at 80° C. for 2 hours. The mixture was recovered by filtration,washed with deionized water and dried at 130° C.

Example 29 (Comparative) Bulk Catalyst Precursor[Ni(6.6)-Mo(1)-W(3)-C(14.5)] with Ex-Situ Addition of Carbon

Example 27 was repeated except that 39 g of the activated carbon (DARCO®G-60) was used instead of silica gel.

Example 30 Catalyst Evaluation—Vacuum Gas Oil Hydroconversion

Bulk catalyst precursor extrudates from Examples 9-11, 15-17 and 25-29were sulfided and evaluated for catalytic activity with a VGO feed in atri-phase fixed bed reactor.

Catalyst precursors were sulfided at 482° F./800 psig (250° C./5.5 MPa)for 5 hours and then ramped to 572° F. (300° C.) at 30° F./hour andsoaked for 5 hours, and then ramped to 650° F./800 psig (343° C./5.5MPa) at 30° F./hour and soaked for 6 hours.

Hydroprocessing conditions included a pressure of 2300 psig, a LHSV of 2h⁻¹, and a H₂ treat gas rate of 4880 SCF/B.

Catalytic activity was compared based on the temperature for 10 ppm Nwith the particle density normalized to 2.5 g/cm³. The results aresummarized in Table 3.

TABLE 3 Additive Particle Added into Density Temperature CatalystNi—Mo—W [g/cm³] [° F.] Example 9 — 2.66 702 Example 10 — 2.38 698Example 11 — 2.19 704 Example 15 TiO₂ 2.09 703 Example 16 TiO₂ 2.16 701Example 17 TiO₂ 2.06 698 Example 25 SiO₂ 2.05 708 Example 26 SiO₂ 1.26712 Example 27 SiO₂ 2.21 710 Example 28 ZrO₂ 1.97 717 Example 29 C 1.60705

The results in Table 3 show that addition of TiO₂ in various amountsdecreases particle density without sacrificing activity as thetemperature needed to reach HDN target stays the same as Ni—Mo—Wcatalyst. In comparison, addition of SiO₂, ZrO₂ and C decreases theactivity although it also decreases particle density.

Example 31 Catalyst Evaluation—Tetralin Hydrogenolysis

Ni—Mo—W bulk catalyst precursors of Examples 10-11 and Ni—Mo—W—Ti bulkcatalyst precursors of Examples 14, 18 and 20-24 were tested fortetralin hydrogenolysis activity in a tri-phase fixed bed reactor asdescribed in Example 9.

The catalyst evaluation conditions included a reactor pressure of 2300psig, a hydrogen feed rate of 3500 SCF/B, and a LHSV of 1 h⁻¹. Thetetralin feed contained 300 wppm sulfur.

Table 4 summarizes the ring opening activity of the catalysts.

TABLE 4 Temp. Yield of Ring Opening Products [%] [° F.] TiO₂ ^((a)) Ex.10 Ex. 11 Ex. 14 Ex. 18 Ex. 20 Ex. 21 Ex. 22 Ex. 23 Ex. 24 640 0.4 1.21.2 0.4 1.5 0.8 0.9 1.0 1.0 1.2 660 0.2 3.6 2.1 2.0 3.7 2.5 1.8 2.9 1.92.9 680 0.2 8.8 4.6 3.4 9.3 6.9 3.9 6.0 3.5 5.8 700 0.2 16.0 8.4 7.218.5 14.2 12.6 13.4 7.4 14.0 720 0.4 26.0 14.1 21.1 34.9 28.8 20.1 24.614.5 23.6 740 0.7 37.6 22.6 37.2 50.2 45.7 29.8 37.7 24.1 32.6^((a))Hydrophilic fumed TiO₂ (AEROXIDE ® P 25, Evonik)

The results in Table 4 indicate that for the ring opening of tetralin,TiO₂ by itself without Ni—Mo—W does not have any activity. TheNi—Mo—W—Ti systems have various levels of activity which depends on thetype of TiO₂ and methods of preparation. Selection of TiO₂ type andpreparation can potentially provide benefits in both low particledensity and enhanced ring opening activity.

Example 32 Catalytic Testing—Hydroconversion of a Straight-RunDiesel/Tetralin Feed

Ni—Mo—W bulk catalyst precursors of Examples 9-11 and Ni—Mo—W—Ti bulkcatalyst precursors of Examples 14, 18 and 22-23 were tested forcatalytic activity in a fixed bed reactor with a 30 vol. % straight-rundiesel/70 vol. % tetralin blend feed. Catalytic activity was comparedbased on conversion of polynuclear aromatic compounds (PNAs).

Catalyst precursors were sulfided as described in Example 8.

Hydroprocessing conditions included a pressure of 1200 psig, a LHSV of 1h⁻¹, and a H₂ gas rate of 3500 SCF/B.

Table 5 summarizes the ring opening activity of the catalysts.

TABLE 5 Conversion of PNAs [%] Temp. Ex. Ex. Ex. Ex. Ex. Ex. Ex. [° F.]9 10 11 14 18 22 23 640 21.4 20.8 21.2 19.9 16.9 20.4 18.7 680 28.4 27.429.1 26.1 24.5 27.9 25.4 700 30.7 29.9 30.2 30.0 26.8 29.4 28.2 720 28.329.8 28.7 28.3 26.2 28.9 27.9 740 24.6 24.7 23.9 23.8 24.5 24.4 23.8 76019.1 19.1 18.1 18.6 18.2 19.6 18.7

The results in Table 5 show that Ni—Mo—W—Ti systems have comparableactivity with Ni—Mo—W systems for hydroconversion of the straight-rundiesel/tetralin feed.

Example 33 (Comparative) Synthesis of Trimetallic Bulk CatalystPrecursor [Ni(1.25)-Mo(1)-Ti(1.12)]

Preparation of Slurry A: 112 g of ammonium heptamolybdate and 57 g ofTiO₂ (Venator S141) were added into 3200 g of deionized water in a 4 Lflask. The pH was adjusted to 9.8 with ammonia water and the solutionheated up to 80° C.

Preparation of Solution B: 230 g of nickel nitrate and 12.6 g of maleicacid were dissolved into 100 g of deionized water.

Solution B was added into Slurry A within 15 minutes. Green precipitateswere formed during the addition of Solution B. The final pH was at6.0-7.0. The slurry was aged with stirring at 80° C. for 4 hours. Afterageing, the product was recovered by filtration, washed with deionizedwater and dried at 130° C.

Example 34 (Comparative) Synthesis of Trimetallic Bulk CatalystPrecursor [Ni(1.1)-W(1)-Ti(1.37)]

Preparation of Slurry A: 182.7 g of ammonium metatungstate and 79 g ofTiO₂ (Venator S141) were added into 3200 g of deionized water in a 4 Lflask. The pH was adjusted to 9.8 with ammonia water and the solutionheated up to 80° C.

Preparation of Solution B: 230 g of nickel nitrate and 12.6 g of maleicacid were dissolved into 100 g of deionized water.

Solution B was added into Slurry A within 15 minutes. Green precipitateswere formed during the addition of Solution B. The final pH was at6.0-7.0. The slurry was aged with stirring at 80° C. for 4 hours. Afterageing, the product was recovered by filtration, washed with deionizedwater and dried at 130° C.

1.-28. (canceled)
 29. A process for hydroprocessing a hydrocarbonfeedstock, the process comprising contacting the hydrocarbon feedstockwith hydrogen in the presence of a bulk catalyst at hydroprocessingconditions to give at least one product, wherein the bulk catalyst is aderived or derivable from a bulk catalyst precursor having a formula of:A_(v)[Ni(OH)_(x)(L)^(p)_(y)]_(z)[Mo_(m)W_(1-m)O₄][Ti(OH)_(n)O_(2-n/2)]_(w) wherein: (i) A is analkali metal cation, a rare earth metal cation, an ammonium cation, anorganic ammonium cation, phosphonium cation, or a combination thereof;(ii) L is an organic compound-based component; and (iii) 0≤y≤−2/p;0≤x<2; 0≤v<2; 0<z; 0<m<1; 0<n<4; 0.1<w/(z+1)<10; wherein the bulkcatalyst precursor is defined by a region of a quaternary phase diagramwherein the region is defined by ten points ABCDEFGHIJ and wherein theten points, on a metal oxide basis (wt. %), are: A (Ni=39, Mo=1, W=41,Ti=20), B (Ni=39, Mo=1, W=72, Ti=20), C (Ni=9, Mo=17, W=54, Ti=20), D(Ni=31, Mo=25, W=24, Ti=20), E (Ni=40, Mo=14, W=26, Ti=20), F (Ni=34,Mo=1, W=36, Ti=30), G (Ni=7, Mo=1, W=63, Ti=30), H (Ni=8, Mo=15, W=48,Ti=30), I (Ni=27, Mo=22, W=21, Ti=30), and J (Ni=35, Mo=12, W=23,Ti=30).
 30. The process of claim 29, wherein the hydroprocessing isselected from the group consisting of hydrodesulfurization,hydrodenitrogenation, hydrodeoxygenation, hydrodemetallation,hydrodearomatization, hydrogenation, hydrogenolysis, hydrotreating,hydroisomerization, and hydrocracking.
 31. The process of claim 29,wherein the hydroprocessing conditions include a temperature of from200° C. to 450° C.; a pressure of from 250 to 5000 psig (1.7 to 34.6MPa); a liquid hourly space velocity of from 0.1 to 10 h⁻¹; and ahydrogen gas rate of from 100 to 15,000 SCF/B (17.8 to 2672 m³/m³). 32.The process of claim 29, wherein the Ti in the bulk catalyst precursoris present, in a metal oxide basis, in an amount ranging from 10-35 wt%.
 33. The process of claim 29, wherein the organic compound-basedcomponent in the bulk catalyst precursor is selected from the groupconsisting of an organic acid or salt thereof, a sugar, a sugar alcohol,and a combination thereof.
 34. The process of claim 29, wherein theorganic compound-based component in the bulk catalyst precursor isselected from the group consisting of glyoxylic acid, pyruvic acid,lactic acid, malonic acid, oxaloacetic acid, malic acid, fumaric acid,maleic acid, tartaric acid, gluconic acid, citric acid, oxamic acid,serine, aspartic acid, glutamic acid, iminodiacetic acid,ethylenediaminetetraacetic acid, fructose, glucose, galactose, mannose,sucrose, lactose, maltose, erythritol, xylitol, mannitol, sorbitol, anda combination thereof.
 35. The process of claim 29, wherein a molarratio of Ni to the organic compound-based component in the bulk catalystprecursor is in a range of 3:1 to 20:1.
 36. The process of claim 29,wherein a molar ratio of Ti/(Ni+Mo+W) in the bulk catalyst precursor isin a range of from 10:1 to 1:10.
 37. The process of claim 29, wherein amolar ratio of Ni/W in the bulk catalyst precursor is in a range of 10:1to 1:10.
 38. The process of claim 29, wherein a molar ratio of W/Mo inthe bulk catalyst precursor is in a range of 100:1 to 1:100.
 39. Theprocess of claim 29, with the bulk catalyst precursor comprising 1 to 15wt. % of a binder.
 40. The process of claim 29, wherein the bulkcatalyst precursor has one or more of the following properties: a BETspecific surface area of from 50 to 250 m²/g; a pore volume of from 0.02to 0.80 cm³/g; and particle density of 1.00 to 3.00 g/cm³.
 41. Theprocess of claim 29, where in the bulk catalyst precursor has beensulfided.
 42. The process of claim 29, wherein the bulk catalystprecursor was prepared using an organotitanium precursor.
 43. Theprocess of claim 40, wherein the organotitanium precursor comprises atitanium alkoxide.
 44. A process for hydroprocessing a hydrocarbonfeedstock, the process comprising contacting the hydrocarbon feedstockwith hydrogen in the presence of a bulk catalyst at hydroprocessingconditions to give at least one product, wherein the bulk catalyst is aderived or derivable from a bulk catalyst precursor having a formula of:A_(v)[Ni(OH)_(x)(L)^(p)_(y)]_(z)[Mo_(m)W_(1-m)O₄][Ti(OH)_(n)O_(2-n/2)]_(w) wherein: (i) A is analkali metal cation, a rare earth metal cation, an ammonium cation, anorganic ammonium cation, phosphonium cation, or a combination thereof;(ii) L is an organic compound-based component; and (iii) 0≤y≤−2/p;0≤x<2; 0≤v<2; 0<z; 0<m<1; 0<n<4; 0.1<w/(z+1)<10; wherein the bulkcatalyst precursor is defined by a region of a quaternary phase diagramdefined by eight points ABCDEFGH and wherein the eight points, on ametal oxide basis (wt. %), are: A (Ni=52.5, Mo=3.5, W=14, Ti=30), B(Ni=38.5, Mo=17.5, W=14, Ti=30), C (Ni=21, Mo=17.5, W=31.5, Ti=30), D(Ni=35, Mo=3.5, W=31.5, Ti=30), E (Ni=60, Mo=4, W=16, Ti=20), F (Ni=44,Mo=20, W=16, Ti=20), G (Ni=24, Mo=20, W=36, Ti=20), and H (Ni=40, Mo=4,W=36, Ti=20).
 45. The process of claim 44, wherein the organiccompound-based component in the bulk catalyst precursor is selected fromthe group consisting of an organic acid or salt thereof, a sugar, asugar alcohol, and a combination thereof.
 46. The process of claim 36,wherein the organic compound-based component in the bulk catalystprecursor is selected from the group consisting of glyoxylic acid,pyruvic acid, lactic acid, malonic acid, oxaloacetic acid, malic acid,fumaric acid, maleic acid, tartaric acid, gluconic acid, citric acid,oxamic acid, serine, aspartic acid, glutamic acid, iminodiacetic acid,ethylenediaminetetraacetic acid, fructose, glucose, galactose, mannose,sucrose, lactose, maltose, erythritol, xylitol, mannitol, sorbitol, anda combination thereof.
 47. The process of claim 44, wherein a molarratio of Ni to the organic compound-based component in the bulk catalystprecursor is in a range of 3:1 to 20:1.
 48. The process of claim 44,wherein a molar ratio of Ti/(Ni+Mo+W) in the bulk catalyst precursor isin a range of from 10:1 to 1:10.
 49. The process of claim 44, wherein amolar ratio of Ni/W in the bulk catalyst precursor is in a range of 10:1to 1:10.
 50. The process of claim 44, wherein a molar ratio of W/Mo inthe bulk catalyst precursor is in a range of 100:1 to 1:100.
 51. Theprocess of claim 44, with the bulk catalyst precursor comprising 1 to 15wt. % of a binder.
 52. The process of claim 44, wherein the bulkcatalyst precursor has one or more of the following properties: a BETspecific surface area of from 50 to 250 m²/g; a pore volume of from 0.02to 0.80 cm³/g; and particle density of 1.00 to 3.00 g/cm³.
 53. Theprocess of claim 44, wherein the bulk catalyst precursor has beensulfided.
 54. The process of claim 44, wherein the bulk catalystprecursor was prepared using an organotitanium precursor.
 55. Theprocess of claim 54, wherein the organotitanium precursor comprises atitanium alkoxide.
 56. The process of claim 44, wherein thehydroprocessing is selected from the group consisting ofhydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation,hydrodemetallation, hydrodearomatization, hydrogenation, hydrogenolysis,hydrotreating, hydroisomerization, and hydrocracking.
 57. The process ofclaim 44, wherein the hydroprocessing conditions include a temperatureof from 200° C. to 450° C.; a pressure of from 250 to 5000 psig (1.7 to34.6 MPa); a liquid hourly space velocity of from 0.1 to 10 h⁻¹; and ahydrogen gas rate of from 100 to 15,000 SCF/B (17.8 to 2672 m³/m³).